EP0049863B1 - Verfahren zur Herstellung von Essigsäure, Acetaldehyd und Ethanol aus Synthesegas - Google Patents

Verfahren zur Herstellung von Essigsäure, Acetaldehyd und Ethanol aus Synthesegas Download PDF

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Publication number
EP0049863B1
EP0049863B1 EP81108025A EP81108025A EP0049863B1 EP 0049863 B1 EP0049863 B1 EP 0049863B1 EP 81108025 A EP81108025 A EP 81108025A EP 81108025 A EP81108025 A EP 81108025A EP 0049863 B1 EP0049863 B1 EP 0049863B1
Authority
EP
European Patent Office
Prior art keywords
temperature
hours
catalyst
acetic acid
ethanol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81108025A
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German (de)
English (en)
French (fr)
Other versions
EP0049863A1 (de
Inventor
Hans-Joachim Dr. Schmidt
Ernst Ingo Dr. Leupold
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0049863A1 publication Critical patent/EP0049863A1/de
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Publication of EP0049863B1 publication Critical patent/EP0049863B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide

Definitions

  • the invention relates to a process for the production of acetic acid, acetaldehyde and ethanol by reacting carbon monoxide with hydrogen in the gas phase over rhodium and possibly promoters containing catalysts at elevated temperatures and pressures.
  • the life of the rhodium catalysts can be improved in a simple manner and in that, in the initial phase of the process, during the heating of the catalyst, the temperature increase in the last 75 to 125 ° C. before the operating temperature is reached continuously or in small steps and performs in a period of 100 to 1000 hours.
  • This measure not only significantly improves the life of the catalysts, but also results in an increased selectivity for the desired oxygen-containing Cz compounds, the selectivity to acetic acid in particular increasing and remaining constant after the operating temperature has been reached, while the selectivity to methane is initially somewhat falls off.
  • the invention therefore relates to a process for the production of acetic acid, acetaldehyde and ethanol by reacting carbon monoxide and hydrogen in the gas phase over catalysts containing rhodium and possibly promoters at elevated temperatures and elevated pressures, which is characterized in that in the initial phase of Process during the heating of the catalyst to the operating temperature T R intended for continuous operation, the temperature increase in the temperature range between T o and T R , where T o is 75 to 125 ° C below T R , continuously or in temperature steps of a maximum of 10 ° C and in a period of 100 to 1000 hours, the temperature being increased by a maximum of 10 ° C in any 10-hour interval.
  • the temperature is preferably increased over a period of 120 to 800 hours.
  • the rate of heating is of crucial importance for the life of the catalyst and the selectivity for the oxygen-containing Cz compounds. It is essential that the temperature increase in the range from 75 to 125 ° C below the operating temperature T R is carried out in small steps of a maximum of 10 ° C and in a period of 100 to 1000 hours.
  • the operating temperature T R is the temperature at which the synthesis gas is converted cheaply and economically to the oxygen-containing compounds acetic acid, acetaldehyde and ethanol in continuous operation. Depending on the catalyst composition, the catalyst preparation, the type and amount of the promoters, and also on the other reaction conditions such as pressure, space velocity and composition of the input gases, it can vary within wide limits. In general, T R is between 200 ° C and 450 ° C, preferably between 250 and 375 ° C. The operating pressure is generally between 1 and 300 bar, preferably between 20 and 200 bar.
  • catalysts which contain 0.1 to 15% by weight, preferably 0.5 to 10% by weight, of rhodium as metal or in a valence stage below three, that is to say as a complex compound of zero-valent rhodium, on a support or as a salt or complex compound of monovalent or divalent rhodium.
  • the catalysts can also contain promoters or activators, in particular magnesium in combination with halide ions, and manganese.
  • substances which influence the selectivity for the individual oxygen-containing products for example iron, zirconium, hafnium, lanthanum, platinum, mercury, molybdenum, tungsten, uranium or thorium.
  • carrier materials with different specific surfaces can be used as carriers Chen are used, preferably those with specific surfaces between 50 and 1000 m 2 / g. Are suitable for.
  • silica silicates, aluminum oxide, titanium dioxide, zirconium dioxide, zeolites, thorium oxide and spinels.
  • the catalyst is brought into the reaction zone and first heated to a temperature To, which is 75 to 125 ° C. below the intended operating temperature T R , at any rate.
  • the further temperature increase from T o to T R is carried out in such a way that heating is carried out continuously or at temperature intervals of at most 10 ° C., the time for the temperature increase from T O to T R being 100 to 1000 hours, preferably 120 to 800 Hours. If, for example, the operating temperature is 300 ° C, after reaching a catalyst temperature that is between 175 and 225 ° C, the temperature is slowly increased further until the operating temperature of 300 ° C is reached after a period of 100 to 1000 hours .
  • synthesis gas or an inert gas such as nitrogen or mixtures of these gases are passed over the catalyst.
  • T o synthesis gas flows under the intended operating pressure over the catalyst, so that in the temperature range between To and T R which is important for the process according to the invention, a temperature rise which is too rapid is avoided when the reaction starts.
  • the conventional fixed bed reactors can be used to carry out the process, it being advantageous to keep the catalyst layer thickness low for better heat dissipation.
  • Reactors with a moving catalyst bed or fluidized bed reactors are also suitable.
  • a preferred embodiment consists in carrying out the reaction in a cycle gas apparatus in which, after the condensable reaction products have been separated off, the unreacted gas mixture is returned to the reactor after addition of fresh synthesis gas.
  • Circular gas apparatuses are those with internal or external gas circulation.
  • the stated space-time yields (STA, in g per liter of catalyst and hour) relate to the total of acetic acid AcOH, acetaldehyde AcH and ethanol EtOH.
  • Residual CO is converted to carbon dioxide and higher molecular weight oxygen-containing compounds.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP81108025A 1980-10-11 1981-10-07 Verfahren zur Herstellung von Essigsäure, Acetaldehyd und Ethanol aus Synthesegas Expired EP0049863B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3038448 1980-10-11
DE19803038448 DE3038448A1 (de) 1980-10-11 1980-10-11 Verfahren zur herstellung von essigsaeure, acetaldehyd und ethanol aus synthesegas

Publications (2)

Publication Number Publication Date
EP0049863A1 EP0049863A1 (de) 1982-04-21
EP0049863B1 true EP0049863B1 (de) 1984-12-12

Family

ID=6114155

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81108025A Expired EP0049863B1 (de) 1980-10-11 1981-10-07 Verfahren zur Herstellung von Essigsäure, Acetaldehyd und Ethanol aus Synthesegas

Country Status (7)

Country Link
US (1) US4351908A (enrdf_load_stackoverflow)
EP (1) EP0049863B1 (enrdf_load_stackoverflow)
JP (1) JPS5793919A (enrdf_load_stackoverflow)
AU (1) AU539682B2 (enrdf_load_stackoverflow)
CA (1) CA1182476A (enrdf_load_stackoverflow)
DE (2) DE3038448A1 (enrdf_load_stackoverflow)
ZA (1) ZA816987B (enrdf_load_stackoverflow)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3203060A1 (de) * 1982-01-30 1983-08-04 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von essigsaeure, acetaldehyd und ethanol
JPH03210428A (ja) * 1990-01-12 1991-09-13 Tlv Co Ltd 液位検出器
GB9819079D0 (en) * 1998-09-03 1998-10-28 Bp Chem Int Ltd Carbonylation process
WO2014114822A1 (es) 2013-01-24 2014-07-31 Abengoa Bioenergía Nuevas Tecnologías, S.A Catalizador de rodio promovido para la conversión selectiva de gas de síntesis en etanol

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4224236A (en) * 1978-04-04 1980-09-23 Hoechst Aktiengesellschaft Process for the manufacture of oxygen-containing carbon compounds from synthesis gas
DE2814427A1 (de) * 1978-04-04 1979-10-18 Hoechst Ag Verfahren zur herstellung sauerstoffhaltiger kohlenstoffverbindungen aus synthesegas
DE2850201A1 (de) * 1978-11-18 1980-06-04 Hoechst Ag Verfahren zur herstellung sauerstoffhaltiger kohlenstoffverbindungen aus synthesegas
EP0004653B1 (de) * 1978-04-04 1981-07-15 Hoechst Aktiengesellschaft Verfahren zur Herstellung sauerstoffhaltiger Kohlenstoffverbindungen aus Synthesegas

Also Published As

Publication number Publication date
JPH0237329B2 (enrdf_load_stackoverflow) 1990-08-23
AU539682B2 (en) 1984-10-11
CA1182476A (en) 1985-02-12
EP0049863A1 (de) 1982-04-21
DE3167733D1 (en) 1985-01-24
DE3038448A1 (de) 1982-06-03
US4351908A (en) 1982-09-28
AU7619981A (en) 1982-04-22
ZA816987B (en) 1982-10-27
JPS5793919A (en) 1982-06-11

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